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At least 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Substrate Partitioning into Protein Macromolecular Frameworks for Enhanced Catalytic Turnover

Spatial partitioning of chemical processes is an important attribute of many biological systems, the effect of which is reflected in the high efficiency of enzymes found within otherwise chaotic cellular environments. Barriers, often provided through the formation of compartments or phase segregation, gate the access of macromolecules and small molecules within the cell and provide an added level of metabolic control. Taking inspiration from nature, we have designed virus-like particles (VLPs) as nanoreactor compartments that sequester enzyme catalysts and have used these as building blocks to construct 3D protein macromolecular framework (PMF) materials, which are structurally characterized using small-angle X-ray scattering (SAXS). Additionally, the highly charged PMFs form a separate phase in suspension, and by tuning the ionic strength, we show positively charged molecules preferentially partition into the PMF, while negatively charged molecules are excluded. This molecular partitioning was exploited to tune the catalytic activity of enzymes enclosed within the individual particles in the PMF, the results of which showed that positively charged substrates had turnover rates that were 8500× faster than their negatively charged counterparts. Moreover, the catalytic PMF led to cooperative behavior resulting in charge dependent trends opposite to those observed with individual P22 nanoreactor particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2011

Mobility Spectrometer Studies on Hydrazine and Ammonia Detection

An airborne vapor analyzer for detecting sub- to low- parts-per-million (ppm) hydrazine in the presence of higher concentration levels of ammonia has been under development for the Orion program. The detector is based on ambient pressure ionization and ion mobility characterization. The detector encompasses: 1) a membrane inlet to exclude particulate and aerosols from the analyzer inlet; 2) a method to separate hydrazine from ammonia which would otherwise lead to loss of calibration and quantitative accuracy for the hydrazine determination; and 3) response and quantitative determinations for both hydrazine and ammonia. Laboratory studies were made to explore some of these features including mobility measurements mindful of power, size, and weight issues. The study recommended the use of a mobility spectrometer of traditional design with a reagent gas and equipped with an inlet transfer line of bonded phase fused silica tube. The inlet transfer line provided gas phase separation of neutrals of ammonia from hydrazine at 50 C simplifying significantly the ionization chemistry that underlies response in a mobility spectrometer. Performance of the analyzer was acceptable between ranges of 30 to 80 C for both the pre-fractionation column and the drift tube. An inlet comprised of a combined membrane with valve-less injector allowed high speed quantitative determination of ammonia and hydrazine without cross reactivity from common metabolites such as alcohols, esters, and aldehydes. Preliminary test results and some of the design features are discussed.

Niu, William↗
DOE OSTI2025

Process intensification in hydrothermal liquefaction of biomass: A review

Hydrothermal liquefaction (HTL) presents a promising pathway for converting wet biomass resources into biofuels, offering significant advantages over conventional methods. However, numerous challenges must be addressed for HTL scale-up, including energy provision for the endothermic process, heat and mass transfer limitations, slurry concentration and pumpability challenges, char and coke formation, and continuous phase separation. This review explores key strategies such as autothermal HTL, which improves process efficiency and reduces external energy requirements by coupling exothermic and endothermic reactions within the same reactor, thereby simplifying reactor design and reducing operational costs. Additionally, multistage HTL processes are highlighted for their ability to optimize biocrude quality and yield by fractionating biomass conversion stages, resulting in higher energy returns on investment and better-quality biocrude. Solvothermal HTL and integration techniques for aqueous phase are also discussed. Furthermore, the HTL patent landscape is discussed to provide insights into current technological advancements. This review aims to offer a comprehensive understanding of process intensification in HTL, highlighting innovative solutions to enhance the efficiency and scalability of the process for sustainable biofuel production.

Biocrude oil↗
DOE OSTI2020

Impact of wet-dry cycling on the phase behavior and compartmentalization properties of complex coacervates

Abstract Wet-dry cycling on the early Earth is thought to have facilitated production of molecular building blocks of life, but its impact on self-assembly and compartmentalization remains largely unexplored. Here, we investigate dehydration/rehydration of complex coacervates, which are membraneless compartments formed by phase separation of polyelectrolyte solutions. Solution compositions are identified for which tenfold water loss results in maintenance, disappearance, or appearance of coacervate droplets. Systems maintaining coacervates throughout the dehydration process are further evaluated to understand how their compartmentalization properties change with drying. Although added total RNA concentrations increase tenfold, RNA concentration within coacervates remains steady. Exterior RNA concentrations rise, and exchange rates for encapsulated versus free RNAs increase with dehydration. We explain these results in light of the phase diagram, with dehydration-driven ionic strength increase being particularly important in determining coacervate properties. This work shows that wet-dry cycling can alter the phase behavior and protocell-relevant functions of complex coacervates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Carnegie Supernova Project I: Spectroscopic analysis of stripped-envelope supernovae

An analysis leveraging 170 optical spectra of 35 stripped-envelope (SE) core-collapse supernovae (SNe) observed by the Carnegie Supernova Project I and published in a companion paper is presented. Mean template spectra were constructed for the SNe IIb, Ib, and Ic subtypes, and parent ions associated with designated spectral features are identified with the aid of the spectral synthesis code SYNAPPS. Our modeled mean spectra suggest the ~6150 Å feature in SNe IIb may have an underlying contribution due to silicon, while the same feature in some SNe Ib may have an underlying contribution due to hydrogen. Standard spectral line diagnostics consisting of pseudo-equivalent widths (pEWs) and blue-shifted Doppler velocity were measured for each of the spectral features. Correlation matrices and rolling mean values of both spectral diagnostics were constructed. A principle component analysis (PCA) was applied to various wavelength ranges of the entire dataset and suggests clear separation among the different SE SN subtypes, which follows from trends previously identified in the literature. In addition, our findings reveal the presence of two SNe IIb subtypes, a select number of SNe Ib displaying signatures of weak, high-velocity hydrogen, and a single SN Ic with evidence of weak helium features. Our PCA results can be leveraged to obtain robust subtyping of SE SNe based on a single spectrum taken during the so-called photospheric phase, separating SNe IIb from SNe Ib with ~80% completion.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Electronic transport properties of spin-crossover polymer plus polyaniline composites with Fe 3 O 4 nanoparticles

Abstract Adding Fe 3 O 4 nanoparticles to composites of [Fe(Htrz) 2 (trz)](BF 4 ) spin-crossover polymer and polyaniline (PANI) drives a phase separation of both and restores the molecular structure and cooperative effects of the spin-crossover polymer without compromising the increased conductivity gained through the addition of PANI. We observe an increased on-off ratio for the DC conductivity owing to an enlarged off state resistivity and a 20 times larger AC conductivity of the on state compared with DC values. The Fe 3 O 4 nanoparticles, primarily confined to the [Fe(Htrz) 2 (trz)](BF 4 ) phase, are ferromagnetically coupled to the local moment of the spin-crossover molecule suggesting the existence of an exchange interaction between both components.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Influence of Carboxymethyl Cellulose as a Thickening Agent for Glauber’s Salt-Based Low Temperature PCM

This work is focused on a novel, promising low temperature phase change material (PCM), based on the eutectic Glauber’s salt composition. To allow phase transition within the refrigeration range of temperatures of +5 °C to +12 °C, combined with a high repeatability of melting–freezing processes, and minimized subcooling, the application of three variants of sodium carboxymethyl cellulose (Na-CMC) with distinct molecular weights (700,000, 250,000, and 90,000) is considered. The primary objective is to optimize the stabilization of this eutectic PCM formulation, while maintaining the desired enthalpy level. Preparation methods are refined to ensure repeatability in mixing components, thereby optimizing performance and stability. Additionally, the influence of Na-CMC molecular weight on stabilization is examined through differential scanning calorimetry (DSC), T-history, and rheology tests. The PCM formulation of interest builds upon prior research in which borax, ammonium chloride, and potassium chloride were used as additives to sodium sulfate decahydrate (Glauber’s salt), prioritizing environmentally responsible materials. The results reveal that CMC with molecular weights of 250 kg/mol and 90 kg/mol effectively stabilize the PCM without phase separation issues, slowing crystallization kinetics. Conversely, CMC of 700 kg/mol proved ineffective due to the disruption of gel formation at its low gel point, hindering higher concentrations. Calculations of ionic concentration indicate higher Na ion content in PCM stabilized with 90 kg/mol CMC, suggesting increased ionic interactions and gel strength. A tradeoff is discovered between the faster crystallization in lower molecular weight CMC and the higher concentration required, which increases the amount of inert material that does not participate in the phase transition. After thermal cycling, the best formulation had a latent heat of 130 J/g with no supercooling, demonstrating excellent performance. This work advances PCM’s reliability as a thermal energy storage solution for diverse applications and highlights the complex relationship between Na-CMC molecular weight and PCM stabilization.

25 ENERGY STORAGE↗
DOE OSTI2022

Observation of solid-state bidirectional thermal conductivity switching in antiferroelectric lead zirconate (PbZrO 3 )

Materials with tunable thermal properties enable on-demand control of temperature and heat flow, which is an integral component in the development of solid-state refrigeration, energy scavenging, and thermal circuits. Although gap-based and liquid-based thermal switches that work on the basis of mechanical movements have been an effective approach to control the flow of heat in the devices, their complex mechanisms impose considerable costs in latency, expense, and power consumption. As a consequence, materials that have multiple solid-state phases with distinct thermal properties are appealing for thermal management due to their simplicity, fast switching, and compactness. Thus, an ideal thermal switch should operate near or above room temperature, have a simple trigger mechanism, and offer a quick and large on/off switching ratio. In this study, we experimentally demonstrate that manipulating phonon scattering rates can switch the thermal conductivity of antiferroelectric PbZrO 3 bidirectionally by –10% and +25% upon applying electrical and thermal excitation, respectively. Our approach takes advantage of two separate phase transformations in PbZrO 3 that alter the phonon scattering rate in different manners. In this study, we demonstrate that PbZrO 3 can serve as a fast (<1 second), repeatable, simple trigger, and reliable thermal switch with a net switching ratio of nearly 38% from ~1.20 to ~1.65 W m –1 K –1 .

25 ENERGY STORAGE↗
DOE OSTI2021

Bridging the thermodynamics and kinetics of temperature-induced morphology evolution in polymer/fullerene organic solar cell bulk heterojunction

The performance of organic solar cells (OSC) critically depends on the morphology of the active layer. After deposition, the active layer is in a metastable state and prone to changes that lead to cell degradation. Here, a high efficiency fullerene:polymer blend is used as a model system to follow the temperature-induced morphology evolution through a series of thermal annealing treatments. Electron microscopy analysis of the nano-scale phase evolution during the early stages of thermal annealing revealed that spinodal decomposition, i.e. spontaneous phase separation with no nucleation stage, is possibly responsible for the formation of a fine scale bicontinuous structure. In the later evolution stages, large polycrystalline fullerene aggregates are formed. Optical microscopy and scattering revealed that aggregate-growth follows the Johnson–Mehl–Avrami–Kolmogorov equation indicating a heterogeneous transformation process, i.e., through nucleation and growth. These two mechanisms, spinodal decomposition vs. nucleation and growth, are mutually exclusive and their co-existence is surprising. This unexpected observation is resolved by introducing a metastable monotectic phase diagram and showing that the morphology evolution goes through two distinct and consecutive transformation processes where spinodal decomposition of the amorphous donor:acceptor blend is followed by nucleation and growth of crystalline acceptor aggregates. Lastly, this unified thermodynamic and kinetic mechanism allows us to correlate the morphology evolution with OSC degradation during thermal annealing.

36 MATERIALS SCIENCE↗
NASA NTRS2016

A Robust, Gravity-Insensitive, High-Temperature Condenser for Water Recovery

Regenerative life support systems are vital for NASA's future long-duration human space exploration missions. A Heat Melt Compactor (HMC) system is being developed by NASA to dry and compress trash generated during space missions. The resulting water vapor is recovered and separated from the process gas flow by a gravity-insensitive condenser. Creare is developing a high-temperature condenser for this application. The entire condenser is constructed from metals that have excellent resistance to chemical attack from contaminants and is suitable for high-temperature operation. The metal construction and design configuration also offer greatest flexibility for potential coating and regeneration processes to reduce biofilm growth and thus enhancing the reliability of the condenser. The proposed condenser builds on the gravity-insensitive phase separator technology Creare developed for aircraft and spacecraft applications. This paper will first discuss the design requirements for the condenser in an HMC system that will be demonstrated on the International Space Station (ISS). Then, it will present the overall design of the condenser and the preliminary thermal test results of a subscale condenser. Finally, this paper will discuss the predicted performance of the full-size condenser and the development plan to mature the technology and enhance its long-term reliability for a flight system.

Chen, Weibo↗
NASA NTRS2013

Multiphase Transport in Porous Media: Gas-Liquid Separation Using Capillary Pressure Gradients International Space Station (ISS) Flight Experiment Development

Advances in the understanding of multiphase flow characteristics under variable gravity conditions will ultimately lead to improved and as of yet unknown process designs for advanced space missions. Such novel processes will be of paramount importance to the success of future manned space exploration as we venture into our solar system and beyond. In addition, because of the ubiquitous nature and vital importance of biological and environmental processes involving airwater mixtures, knowledge gained about fundamental interactions and the governing properties of these mixtures will clearly benefit the quality of life here on our home planet. The techniques addressed in the current research involving multiphase transport in porous media and gas-liquid phase separation using capillary pressure gradients are also a logical candidate for a future International Space Station (ISS) flight experiment. Importantly, the novel and potentially very accurate Lattice-Boltzmann (LB) modeling of multiphase transport in porous media developed in this work offers significantly improved predictions of real world fluid physics phenomena, thereby promoting advanced process designs for both space and terrestrial applications.This 3-year research effort has culminated in the design and testing of a zero-g demonstration prototype. Both the hydrophilic (glass) and hydrophobic (Teflon) media Capillary Pressure Gradient (CPG) cartridges prepared during the second years work were evaluated. Results obtained from ground testing at 1-g were compared to those obtained at reduced gravities spanning Martian (13-g), Lunar (16-g) and zero-g. These comparisons clearly demonstrate the relative strength of the CPG phenomena and the efficacy of its application to meet NASAs unique gas-liquid separation (GLS) requirements in non-terrestrial environments.LB modeling software, developed concurrently with the zero-g test effort, was shown to accurately reproduce observed CPG driven gas-liquid separation phenomena. The design and fabrication of a micropost plate-lamina Hele-Shaw (HS) cell was performed which served as a computationally attainable geometric structure facilitating direct comparison between physical phenomena observed in our laboratory and the LB software predictions.

Wheeler, Richard R., Jr.↗
DOE OSTI2022

Correlative image learning of chemo-mechanics in phase-transforming solids

We report constitutive laws underlie most physical processes in nature. However, learning such equations in heterogeneous solids (for example, due to phase separation) is challenging. One such relationship is between composition and eigenstrain, which governs the chemo-mechanical expansion in solids. Here we developed a generalizable, physically constrained image-learning framework to algorithmically learn the chemo-mechanical constitutive law at the nanoscale from correlative four-dimensional scanning transmission electron microscopy and X-ray spectro-ptychography images. We demonstrated this approach on Li X FePO 4 , a technologically relevant battery positive electrode material. We uncovered the functional form of the composition–eigenstrain relation in this two-phase binary solid across the entire composition range (0 ≤ X ≤ 1), including inside the thermodynamically unstable miscibility gap. The learned relation directly validates Vegard’s law of linear response at the nanoscale. Our physics-constrained data-driven approach directly visualizes the residual strain field (by removing the compositional and coherency strain), which is otherwise impossible to quantify. Heterogeneities in the residual strain arise from misfit dislocations and were independently verified by X-ray diffraction line profile analysis. Our work provides the means to simultaneously quantify chemical expansion, coherency strain and dislocations in battery electrodes, which has implications on rate capabilities and lifetime. Broadly, this work also highlights the potential of integrating correlative microscopy and image learning for extracting material properties and physics.

36 MATERIALS SCIENCE↗
NASA NTRS2013

Characterizing Uranus with an Ice giant Planetary Origins Probe (Ice-POP)

We now know from studies of planetary transits and microlensing that Neptune-mass planets are ubitquitous and may be the most common class of planets in the Galaxy. As such it is crucial that we understand the formation and evolution of the ice giant planets in our own solar system so that we can better understand planet formation throughout the galaxy. An entry probe mission to Uranus would help accomplish this goal. In fact the Planetary Decadal Survey recommended a Uranus orbiter with entry probe but did not explore in detail the specifications for the entry probe. NASA Ames is currently studying thermal protection system requirements for such a mission and this has led to questions regarding the minimum interesting science payload of such an entry probe. The single most important in-situ measurement for an ice giant entry probe is a measurement of atmospheric composition. For Uranus this would specifically include the methane and noble gas abundances. An in situ measurement of the methane abundance, from below the methane cloud, would constrain the atmospheric carbon abundance, which is believed to be roughly 30 to 50 times solar. There are hints from the transiting planets that extrasolar ice giants show comparable or even greater enhancements of heavy elements compared to their primary stars. However the origin of this carbon enhancement is controversial. Is Uranus a "failed core" of a larger gas giant or was the atmosphere enhanced by accretion of icy planetesimals' Constraining atmospheric abundances of C and perhaps S or even N from below 5 bars would provide badly needed data to address such issues. A measurement of the N abundance would provide clues on the origin of the planetesimals that formed Uranus. Low N-abundance indicates planetesimals from 'warmer' regions where N was mainly in form of NH3, whereas a strong enrichment could indicate planetesimals / cometary material from the colder outer regions of the nebula. Furthermore CO and HCN have been detected in Neptune but not in Uranus. A measurement of the abundance of either would constrain the source mechanisms for these molecules (exogenic or internal). A major surprise from the Galileo Entry Probe was that the heavier noble gases Ar, Kr, and Xe are enhanced in Jupiter's atmosphere at a level comparable to what was seen for the chemically active volatiles N, C, and S. It had been generally expected that Ar, Kr, and Xe would be present in solar abundances, as all were expected to accrete with hydrogen during the gravitational capture of nebular gases. Enhanced abundances of Ar, Kr, and Xe is equivalent to saying that these noble gases have been separated from hydrogen. There are several mechanisms that could accomplish this but these hypotheses require further testing. Measurement of noble gas abundances in an ice giant would constrain the planetary formation and nebular mechanisms responsible for this enhancement. Standard three-layer models of Uranus find that the outer, predominantly H/He layer of Uranus does not reach pressures high enough (approximately 1 Mbar) for H2 to transition to liquid metallic hydrogen. However, valid models can also be constructed with a smaller intermediate water-rich layer, with hydrogen then reaching the metallic hydrogen phase. If this occurs, He should phase separate from the hydrogen and ``rain out," taking along a substantial abundance of Ne, as suggested for Jupiter (and likely also for Saturn). Hence He and Ne depletions could be probes of the planet's structure in the much deeper interior. A determination of Uranus' atmospheric abundances, particularly of the noble gasses, is thus critical to understanding the formation of Uranus, and giant planets in general. These measurements can only be performed with an entry probe. The second key measurement would be a temperature-pressure sounding to provide ground truth for remote measurements of atmospheric temperature and composition and to constrain the internal heat flow. This would also establish that the methane abundance measurements have indeed been made below any possible methane cloud. Finally an ultra stable oscillator would measure wind speeds and constrain atmospheric dynamics. In our presentation we will discuss the importance of all of these measurements and argue that an entry probe is a crucial component of any ice giant mission.

Marley, Mark S.↗
DOE OSTI2024

Laser-induced quenching of metastability at the Mott insulator to metal transition

There is growing interest in strongly correlated insulator thin films because the intricate interplay of their intrinsic and extrinsic state variables causes memristive behavior that might be used for biomimetic devices in the emerging field of neuromorphic computing. Here, in this study, we find that laser irradiation tends to drive V 2 ⁢O 3 from supercooled/superheated metastable states toward thermodynamic equilibrium, most likely in a nonthermal way. We study thin films of the prototypical Mott-insulator V2⁢O3, which show spontaneous phase separation into metal-insulator herringbone domains during the Mott transition. Here, we use low-temperature microscopy to investigate how these metal-insulator domains can be modified by scanning a focused laser beam across the thin film surface. We find that the response depends on the thermal history: When the thin film is heated from below the Mott transition temperature, the laser beam predominantly induces metallic domains. On the contrary, when the thin film is cooled from a temperature above the transition, the laser beam predominantly induces insulating domains. Very likely, the V 2 ⁢O 3 thin film is in a superheated or supercooled state, respectively, during the first-order phase transition, and the perturbation by a laser beam drives these metastable states into stable ones. This way, the thermal history is locally erased. Our findings are supported by a phenomenological model with a laser-induced lowering of the energy barrier between the metastable and equilibrium states.

Materials Science↗
NASA NTRS2013

Ar-40/Ar-39 Ages for Maskelynites and K-Rich Melt from Olivine-Rich Lithology in (Kanagawa) Zagami

We report Ar/Ar release patterns for small maskelynite grains and samples of a K-rich phase separated from the basaltic shergottite Zagami. The purpose of the work is to investigate the well-known discrepancy between published Ar/Ar ages of Zagami, >200 Ma, and its age of approx. 170 Ma as determined by other methods [1-6]. Niihara et al. [7] divide less abundant darker material present in Zagami into an olivine-rich lithology (ORL), from which most of our samples came, and a pyroxene-rich one (Dark Mottled-Lithology: DML) [8, 9]. ORL consists of vermicular fayalitic olivine, coarse-grained pyroxene, maskelynite, and a glassy phase exceptionally rich in K (up to 8.5 wt%), Al, and Si, but poor in Fe and Mg. The elemental composition suggests a late-stage melt, i.e., residual material that solidified late in a fractional crystallization sequence. Below we refer to it as "K-rich melt." The K-rich melt contains laths of captured olivine, Ca-rich pyroxene, plagioclase, and opaques. It seemed to offer an especially promising target for Ar-40/Ar-39 dating.

Park, J.↗
NASA NTRS2014

Ambulation Increases Decompression Sickness in Spacewalk Simulations

Musculoskeletal activity has the potential to both improve and compromise decompression safety. Exercise enhances inert gas elimination during oxygen breathing prior to decompression (prebreathe), but it may also promote bubble nuclei formation (nucleation), which can lead to gas phase separation and bubble growth and increase the risk of decompression sickness (DCS). The timing, pattern and intensity of musculoskeletal activity and the level of tissue supersaturation may be critical to the net effect. Understanding the relationships is important to evaluate exercise prebreathe protocols and quantify decompression risk in gravity and microgravity environments. Data gathered during NASA's Prebreathe Reduction Program (PRP) studies combined oxygen prebreathe and exercise followed by low pressure (4.3 psi; altitude equivalent of 30,300 ft [9,235 m]) microgravity simulation to produce two protocols used by astronauts preparing for extravehicular activity. Both the Phase II/CEVIS (cycle ergometer vibration isolation system) and ISLE (in-suit light exercise) trials eliminated ambulation to more closely simulate the microgravity environment. The CEVIS results (35 male, 10 female) serve as control data for this NASA/Duke study to investigate the influence of ambulation exercise on bubble formation and the subsequent risk of DCS. METHODS Four experiments will replicate the CEVIS exercise-enhanced oxygen prebreathe protocol, each with a different exception. The first of these is currently underway. Experiment 1 - Subjects complete controlled ambulation (walking in place with fixed cadence and step height) during both preflight and at 4.3 psi instead of remaining nonambulatory throughout. Experiment 2 - Subjects remain non-ambulatory during the preflight period and ambulatory at 4.3 psi. Experiment 3 - Subjects ambulate during the preflight period and remain non-ambulatory at 4.3 psi. Experiment 4 - The order of heavy and light exercise employed in the CEVIS protocol is reversed, with the light exercise occurring first (subjects remain non-ambulatory throughout). Decompression stress is assessed with non-invasive ultrasound during each of 14 epochs of a 4 hour simulated spacewalk at 4.3 psi; aural Doppler is used to monitor bubbles (Spencer grade 0-IV scale) passing through the pulmonary artery, and two-dimensional echocardiographic imaging is used to look for left ventricular gas emboli (LVGE; the presence of which is a test termination criterion). Venous blood is collected at baseline and twice following repressurization to determine if the decompression stress is correlated with microparticles (cell fragments) accumulation. The plan is to test 25-50 subjects in each experiment. Fisher Exact Tests (one-tailed) are used to compare test and control groups. Trials are suspended when the DCS or grade IV VGE observations reach 70% confidence of DCS risk >15% and grade IV VGE risk >20%. RESULTS Experiment 1 was concluded with 20 complete trials (15 male, 5 female) since the statistical outcome would not change with five additional trials. The observed DCS was significantly greater in Experiment 1 than in CEVIS trials (4/20 [20%] vs. 0/45 [0%], respectively, p=0.007), as was the frequency of peak grade IV VGE (6/21 [29%; including one additional subject that presented grade IV VGE but whose trial was ended before completion when LVGE were observed] vs. 3/45 [7%], respectively, p=0.024). Experiment 3 trials are now underway, with 11 trials completed (10 male, 1 female). Preliminary results indicate no difference in observed DCS between Experiment 3 and CEVIS trials (1/11 [9%] vs. 0/45 [0%], respectively, p=0.196), or between Experiment 3 and Experiment 1 trials (p=0.405). The frequency of peak grade IV VGE in Experiment 3 (2/11 [18%]) did not differ from CEVIS or Experiment 1 trials (p=0.251 and p=0.425, respectively). Microparticle patterns are widely variable and still under analysis. DISCUSSION The results of the Experiment 1 trials support the thesis that decompression stress is increased by ambulation exercise, given the higher incidence of DCS and grade IV VGE when compared to the non-ambulatory PRP CEVIS trials. Experiment 3 trials are incomplete, but suggest that the effect of ambulation during ground level preflight oxygen breathing alone, when subjects are undersaturated with inert gas, may not differ in risk from ambulation at both preflight and spacesuit pressures, the latter when subjects are supersaturated with inert gas. Further trials are needed to confirm the relative effects of ambulation in undersaturated vs. supersaturated states and to determine whether light exercise facilitates the removal of heavy exercise-induced nucleation (Experiment 4).

Pollock, N. W.↗
DOE OSTI2023

Reactive flash sintering of TiZrN and TiAlN ternary metal nitrides

Here, this study demonstrated the reactive flash sintering (RFS) for two powder mixtures: TiN-ZrN (both conducting) and AlN-TiN (TiN conducting but AlN insulating), targeting ternary metal nitrides (TMN) of Ti 0.5 Zr 0.5 N and Ti 0.5 Al 0.5 N, respectively. A constant volage and pressure (e.g., 8 V DC, ∼15 MPa) at room temperature triggered the flash (current density up to 27 A/mm 2 ) without pre-heating, and the entire RFS process finished in a few minutes. For TiZrN, the flash was instantaneous whereas for TiAlN, there was a long incubation before the flash followed by a quick and dramatic flash. Both conventional ex situ XRD and in situ synchrotron study had been carried out. They showed a uniform Ti 0.57 Zr 0.43 N solution formed in RFS and persisted upon cooling, while (Ti, Al) N solid solution formed at high temperature was not stable and likely went through a very quick phase separation in the cooling process. The final products from RFS had been characterized using SEM/EDS for microstructure. Both TiZrN and TiAlN were dense. Distribution of Ti, Zr, and N was uniform for TiZrN; for TiAlN, Ti and N distribution was uniform, while association of Al with oxygen was observed. TGA-DSC revealed the onset oxidation temperature for TiZrN was comparable to TiN and ZrN, while it was higher by ∼200 °C for TiAlN, likely due to the formation of Al 2 O 3 . In terms of mechanical properties such as hardness or fracture toughness, forming a single-phase solid solution (like TiZrN) does not offer obvious benefits. while large grain size from RFS seemed to be unfavorable. Future optimization of RFS condition and in-depth study by both experiments and simulation are needed to fully understand the composition-processing-structure-property relationships for such TMN from the reactive flash sintering process.

Flash Sintering↗
DOE OSTI2021

Compositional patterning in irradiated alloys: Effective potentials and effective interfacial energy

Compositional patterning (CP) in binary alloys during energetic particle irradiation is studied using a kinetic model that considers two competing kinetic processes, a thermally activated one promoting macroscopic phase separation (MPS) of the concentration field c(r,t) and a forced one resulting in finite-range random atomic mixing. The forced mixing is modeled by a Gaussian relocation distribution with a characteristic distance R. A series of approximate kinetic models are introduced by expanding the mixing function into a series of n terms, thus replacing the non-local evaluations of the concentration field c(r'-r,t) by local derivatives of c(r,t). This approach makes it possible to obtain exact effective potentials and build steady-state diagrams for each order-n model. Phase field (PF) simulations using these order-n models reveal that near the onset of patterning, phase evolution is accurately described using an order-3 model, which changes smoothly from an extended Cahn-Hilliard free energy in the MPS regime to a one-mode Swift-Hohenberg functional in the CP regime. Deeper into the patterning regime, higher-order models are required to achieve convergence, yielding square-like concentration profiles characteristic of a strong segregation regime. These higher-order effective free energies are analogous to multimodal Swift-Hohenberg functionals. Here, a new definition for the effective interfacial energy is proposed in the CP regime, since the interfacial area is no longer an excess quantity in that regime, precluding the use of the standard thermodynamic definition of interfacial energy.

36 MATERIALS SCIENCE↗